Coloration of cellulose derivatives



Patented Feb. 9, 1932 v UNITED STATES PATENT: OFFICE- GEORGE HOLLAND ELLIS, HENRY CHARLES OLPIN', AND ERIC EATON WALKER, OF

SPONDON, NEAR DERBY, ENGLAND, ASSIGNORS TO CEIAN'ESE CORPORATION 01' AMERICA, A CORPORATION OF DELAWARE OOIDRATION OF OELLULOSE DERIVATIVES We Drawing. Applicationfiled January 8, 1929, Serial No. 330,186, and in Great Britain Tannery 80, 1988.

This invention relates to the dyeing, printing, stencilling or otherwise coloring of yarns, threads, woven or knitted fabrics or other materials made with or containing cellulose acetate or other organic esters of cellulose, for example cellulose formate, propionate or butyrate or the products obtained by the treatment of alkalized cellulose with esterifying agents (e. g. the product known as immunized cotton obtained with p-toluene sulphochloride), or made with or containing cellulose ethers, for instance methyl, ethyl or benzyl cellulose or the condensation products oi? cellulose and glycols or other polyhydric alcohols, all of which cellulose derivatives are hereinafter referred to as organic substi tution derivatives of cellulose.

In the production of ice-colors upon cotton.

tization on the fibre or material and treat-- ment with a developer, (5) application of the developer component (e. g. phenolic compound) followed b development with a diazo solution and (it) application of amine and developer together or separately and subsequent diazotization on the fibre or material.

lln methods (6) and (a), i. e. when the developer component is applied before any diazotization hastaken place, it is essential in order to obtain good colorations that the developer com onent should be capable of being absorbs substantively by the fibre. It is found that this is not possible with the usual solutions of the alkali salts of hydroxynaphthoic acid arylides. If: the impregnation be entirely mechanical the color formation is almost entirely superficial owing to this lackof absorption, so that the color rubs 0E badly and is. also fugitive to washing, etc. If rinsing follows the impregnation with the alkali salt of the arylide before development in the diazonium liquor, the arylide compound is largely removed.

We have discovered that these dificulties may be surmounted and useful colorations free from the above mentioned defects achieved by applying the hydroxynaphthoic oring materials made with or containing cel lulose acetate or other organic substltution" derivatives of cellulose by applying dispersions of one or 'morefree hydroxynaphthoic acid arylides either alone or together with a diazotizable amine and subsequently developing with a dia zo-body or diazotizing on the fibre or material.

The dispersions of the hydroxynaphthoic acid arylides may be obtained by any suitable method, for example by fine milling or grinding (so-called colloid milling) if desirable with the aid of dispersators and/or protective colloids; by dissolving in a solvent and mixing with water containing or not containing protective colloids or drspersators,

:e. g. soaps; or by treating the arylides with dispersators, for example as described in prior U. S. Patents Nos. 1,618,413, 1,618,414, 1,690,481, 1,694,413 and 1,716,721 and U. s. applications 1,694,413, 1,690,481, 152,517 filed 3rd December 1926, 134,138 filed 7th September 1926. As examples of suitable disper'sators the following may be mentioned :higher fatty acids or sulphonated or other derivatives thereofi containing saltforming groups, for example sulphoricinoleic acid or other sulphated fatty acids, or salts of such acids or derivatives, for instance their alkali or ammonium salts, such acids, derivatives or compounds being generically referred to in U. S. Patent No. 1,618,413 as bodies of oily or fatty characteristics; sulpho-aromatiefatty acids, for example sult pho-benzene stearic acid (Twitchell reagent), sulpho-phenol-stearic acid, sulphonaphthalene stearic acid, and sulpho-naphthalene ricinoleic acid, or salts of such bodies; carbocyclic compounds containing in their structure one or more salt-forming groups, e. g. naphthenic acids or other carboxylic or sulphonic acids of the cycloparaflins, phenols, sulphonic acids, carboxylic acids, phenol sulphonic acids, sulphonated naphtha- Ilene-formaldehyde condensation products or other derivatives of the benzene, naphthalene or anthracene series or other derivatives of saturated or non-saturated cyclic hydrocarbons containing one or more salt-forming groups, or sodium or other salts of any such compounds; and soluble resin soaps or sodium or other soluble salts or soaps of resin acids.

As examples of arylides we may mention the anilide, m-nitranllide and p-anisidide of 3-(23) hydroxynaphthoic acid as being particularly usefulin connection with the coloring of cellulose acetate, but it will be understood that the invention is not limited thereto but covers the application of any hydroxynaphthoic acid arylide.

The amines, for application as such or in the diazotized form, may be simple amino bases or aminoazo compounds and in addition to the amino (or diazo) group may have any or a plurality of any other desired sub stituents, for example nitro, halogen, alliyl;

* aryl, aralkyl, alkoxy, aryloxy, acylamlno,

acylamide or thiazol groups. The following are given as examples of suitable diazotizable amino bases but the listing of these examples implies no limitation of the invention thereto Amino derivatives of benzene Aniline.

p-nitraniline.

o-chloraniline.

m-toluidine.

in-nitro-p-toluidine.

a-amino diphenyl.

Benzidine.

Dianisidine.

4-amino-diphehyl methane.

4:.4'-diamino-diphenyl methane.

o-anisidine. p-nitro-o-anisidine. p-amino-acetanilide.

1 amino-3-p-toluenesulphon zene.

4-amino-diphenylether. 3 nitroi-amino-diphenylether.' Dehydrothio-P'toluidine. 1 l-p-amino phenyl-3-methyl-5-pyrazolone.

Amino derivatives 0 f naphthalene a-naphth ylamine. fi-naphthylamine. O 4-nitro-l-naphthylamine.

amino ben- 8-chlor-l-naphthylamine.

l-amino-2-methoxy-naphthalene.

1.5-naphthylene diamine. V

1-amino-4-acetylamino-naphthalene.

l amino--p-toluenesulphonamino naphthalene.

Amino derivatives of aeobenzene Aminoazobenzene. Aminoazotoluene. 4-nitro-4.-aminoaz0benzene.- 4-chlor-2-nitro-4'-aminoazobenzene. 2-nitro-2. 4:. dimethyl-4'-aminoazobenzene. 4.4 diaminoazobenzene. 2.4-dinitro-3'.6-dimethyl-4-aminoazobenzene. 4-dimethyIamino-4'-amin0azobenzen I l-methoxyl'-aminoazobenzene.

4-phenoxy-2-methyl-4-aminoazobenzene.

Other amino aeo compounds Aminoazonaphthalene. Benzene-azo-a-naphthylamine. Z-methoxybenzene-azo-a-naphthylamine. 4-aminobenzene-azo-a-naphthylamine.

. 4c-acetylaminobenzene-azo -a -naphthylam- 1ne.

4-nitro-2-methoxy benzene azo-a -naphthylamine.

3.5-dinitro-2-hydroxybenzeneazo-a-naphthylamine.

2.4-dinitr0benzene-azo-a-naphthylamine. 4 chlornaphthalene-azo 1-amino-2-methoxynaphthalene.

Anthmguz'none derivatives l-aminoanthraquinone.

"1-amino-2-methylanthraquinone.

Q-aminoanthraquinone.

1-amino-4-hydroxyanthraquinone.

1.5-diaminoanthraquinone.

1.8-diaminoanthraquinone.

1-amino-4-acetylaminoanthraquinone.

1-amino-4-bromanthraquinone.

The dispersions, of the arylides and the amino compounds or diazo bodies may be applied by any suitable dyeing, printing or stencilling methods. If the amine is to be applied together with the arylide, it may be incorporated in the form of the free base in the dispersion of the arylide. If the amineis to be applied separately it may be applied as a dispersion of the free base or by any other suitable method.

The followingexamples cit-procedure according to the present inve tion are intended to be purely illustrative and in'no Way limitative Example 1 I *3 kilos of the m-nitranilide of ,B-hydroxynaphthoic acid (known commercially as naphthol'ASBS) are reduced to a fine state rea ism of subdivision by any suitable means, such for example as precipitation from caustic alkaline solution by acid, or by wet grinding in a so-called colloid mill. The paste thus formed is intimately mixed with 9 kilos of Turkey red oil heated to C. diluted suitably with boiling soft water, and passed through a filter cloth into a dyeing machine containing; 3000 litres of soft water. The goods are then entered, and the bath raised to 80 C. during hour and maintained at that temperature for a further hour. The goods are then washed oil, and entered into a 3000 litre bath containing 2 kilos of p-nitraniline diazotized by usual methods excess of mineral acid being neutralized by addition of the calculated quantity of sodium acetate. The goods are treated for 2 hours at normal temperature, rinsed well, soaped, washed ott, and dried or otherwise treated as requisite.

Example 2 To dye kilos of cellulose acetate knit fabric a fast navy blue shade 3 kilos of a-nitro-EZ-methoxybenzene-azo-a naphthylamine, 10% paste, suitably dispersed in 1 kilo 50% Turkey red oil, and 3 kilos m-nitranilide of B-hydroxynapthoic acid, dispersed as in example 1, are added through a filter cloth to a dyeing machine containing 3000 litres of soft water. The goods are entered into the cold bath, which is raised to 80 C. during hour and maintained at that temperature for a further 1% hours. They are now washed off, and en tered into a cold bath (30:1 on the goods) containing 2 grams per litre of sodium nitrite and 6 cos. per litre of hydrochloric acid 28 Tw. After working for hour the bath is rendered just alkaline to litmus by cautious addition of soda ash, and the goods worked a further hour. After well washing and soaping, the goods are dried, or otherwise treated as requisite.

/Vhat we claim and desire to secure by Letters Patent is T. Tn the method of coloring materials comprising organic substitution derivatives of cellulose with hydroXy-naphthoic arylide colors in which the arylide component is applied before diazotization takes place, the step of applying the hydroXy-naphthoic arylide in the free state in the form of a dispersion.

2. Tn the method of coloring materials comprising cellulose acetate with ,B-hydroxynaphthoic arylide colors in which the arylide component is applied before diazotization takes place, the step of applying the ,B-hydroXy-naphthoic arylide in the free state in the form of a dispersion.

3. Tn coloring materials comprising cellulose acetate with hydroXy-naphthoic arylide colors, applying the hydroXy-naphthoic aryltranilide of ,B-hydroxynaphthoic acid in the free state in the form of a dispersion.

5. Tn coloring materials comprising cellulose acetate with hydroXy-naphthoic arylide colors, applying the m-nitranilide of B-hydroxynaphthoic acid in the free state in the form of a dispersion and then applying a diazo solution.

6. Tn coloring materials comprising celluv lose acetate,applying a hydroXy-naphthoic arylide in the free state in the form of a dispersion and an amine and subsequently diazotizing".

7. Tn coloring materials comprisin cellulose acetate, applying an amine an a hydroXy-naphthoic arylide in the free state together in the form of a dispersion and subsequently diazotizing.

8. Tn coloring materials comprising cellulose acetate, applying B-hydroXy-naphthoic arylide in the free state in the form of a dispersion together with an amine and subsequently diazotizing.

9. Tn coloring materials comprising cellulose acetate, applying the meta-nitranilide of B-hydroxy-naphthoic acid in the free state together with an amine in the form of a dispersion and subsequently diazotizing.

Tn testimony whereof, we have hereunto subscribed our names.

GEORGE HOLLAND ELLIS. HENRY CHARLES OLPTN. ERTG EATON WALKER. 

